CN102066462A - 聚酰胺、包含该聚酰胺的组合物、以及它们的用途 - Google Patents
聚酰胺、包含该聚酰胺的组合物、以及它们的用途 Download PDFInfo
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- CN102066462A CN102066462A CN2009801233148A CN200980123314A CN102066462A CN 102066462 A CN102066462 A CN 102066462A CN 2009801233148 A CN2009801233148 A CN 2009801233148A CN 200980123314 A CN200980123314 A CN 200980123314A CN 102066462 A CN102066462 A CN 102066462A
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- polymeric amide
- diacid
- composition
- acid
- copolyamide
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Abstract
本发明涉及包含至少一种对应于通式X.Y的重复单元的聚酰胺,在该通式中:X代表脂环族二胺,Y代表选自十二烷(C12)二酸、十四烷(C14)二酸和十六烷(C16)二酸的脂族二羧酸,所述聚酰胺的特征在于所述二羧酸包含根据标准ASTM D6866确定的能再生来源的有机碳。本发明还涉及包含该聚酰胺的组合物以及该聚酰胺和所述组合物的用途。
Description
本发明涉及聚酰胺、其制备方法、以及其用途,特别是在各种物品,例如常用品(staple),诸如隐形眼镜,眼镜片,电气、电子或机动车配件,外科材料,包装物或运动器材的制造中的用途。
本发明还涉及包含这种聚酰胺的组合物和该组合物的用途,特别是该组合物在以上列出的全部或部分物品的制造中的用途。
通过二胺和二酸的缩聚获得的透明无定形聚酰胺是目前已知的。这种聚酰胺是特别有利的,因为它们表现出很多种机械性能(例如冲击强度、拉伸强度和/或压缩强度、对外部侵袭(例如热、化学品、UV辐射等)的高耐受性)以及透明性。
因此,已经出现了基于聚酰胺的物品,例如眼镜架、各种容器、机动车配件、外科材料、包装物或运动器材。
适合用于制造这种类型物品的透明无定形聚酰胺已经具体地描述于本申请人的文献EP1595907和US2005/0272908中。这些聚酰胺是通过至少一种脂环族二胺和至少50摩尔%的十四烷二酸的缩聚获得的,也可使用选自脂族二羧酸、芳族二羧酸和脂环族二羧酸的一种或多种其它额外的二羧酸。
这些聚酰胺不仅表现出以上列出的所有性质,而且还表现出典型地为约130℃~160℃的相对高的玻璃化转变温度Tg。
然而,近些年来对环境的关注有利于这样的材料的开发:该材料通过在其制造中特别限制得自石油工业的原材料的供应而尽可能满足可持续发展的需要。
因此,本发明的目的是提供具有至少一些前述机械性能并同时在其结构中包含得自能再生原材料的单元的聚酰胺。
通过阅读以下描述及实施例,本发明的其它特征、方面、目的和优点将变得更清楚。
通常,聚酰胺包含至少两个相同或不同的重复单元,这些单元由两种相应的单体或共聚单体形成。因而,聚酰胺由选自氨基酸、内酰胺、和/或二羧酸和二胺的两种或更多种单体或共聚单体制备。
本发明的目的通过包含至少一种对应于以下通式的重复单元的聚酰胺实现:
X.Y
在该通式中:
X代表脂环族二胺,和
Y代表选自十二烷(C12)二酸、十四烷(C14)二酸或十六烷(C16)二酸的脂族二羧酸,
所述聚酰胺的特征在于所述脂族二羧酸包含根据标准ASTM D6866确定的能再生来源的有机碳(也称作生物来源碳)。
因此,当本发明聚酰胺仅包含相同的X.Y单元时,其可为均聚酰胺。当本发明聚酰胺包含至少两种不同的X.Y单元时,其也可为共聚酰胺。通常,共聚酰胺表示为X.Y/Z,从而可区分不同共聚单体。优选地,本发明聚酰胺为均聚酰胺。
能再生原材料是动物或植物性的自然资源,以人类的寿命来看,可在短期内再次建立这种原材料的储存。具体地说,对于该储存,有必要使再生速度能够与其消耗速度相当。
通常,聚酰胺的耐久性是其基本性质之一。聚酰胺通常用于预期寿命为至少约十年的应用中。当在这些聚酰胺的制造中使用能再生来源的原材料(例如植物油(如蓖麻油或棕榈油))时,可认为,由于最初在光合作用期间(在植物的情况下)从大气中汲取的一定量的CO2被长期固定在材料中,因此,至少在聚酰胺制品的整个寿命期间其不参与碳循环。
相反地,化石来源的聚酰胺在它们的寿命期间不捕集大气中的CO2(例如在光合作用期间所捕集的CO2)。在寿命结束时(例如焚烧期间),聚酰胺可每吨聚酰胺释放约2.5吨化石CO2(其以前已经被捕集在化石资源中)。
当使用化石原材料制造这些聚酰胺时,在该材料的寿命结束时产生这样的影响——将从碳循环中移出的且自经过约几百万年的时间跨度变成化石后的碳再次投入到碳循环中。换句话说,所述碳将参与到循环中,导致失衡。于是,这些现象促进累积效应并由此促使温室效应的提高。
对于本发明的聚酰胺,使用能再生来源的原材料代替化石来源的原材料有助于将在寿命结束时可能释放的化石CO2的量减少至少44%,其中,所述CO2源自原材料的基于碳的结构。
不同于得自化石材料的材料,能再生的或生物来源的原材料包含14C。得自活生物体(动物或植物)的所有碳样品实际上是下列三种同位素的混合物:12C(占约98.892%)、13C(约1.108%)和14C(痕量:1.2×10-10%)。活组织的14C/12C之比与大气的14C/12C之比相一致。在自然环境中,14C以两种主要形式存在:无机形式(即二氧化碳气体(CO2)的形式)和有机形式(即结合到有机分子中的碳的形式)。
在活生物体中,14C/12C之比通过新陈代谢而保持恒定,因为碳不断地与外部环境进行交换。由于大气中的14C的比例是恒定的,当生物体存活时,生物体中的14C的比例也是恒定的,因为生物体以与其吸收环境中的12C一样的方式吸收14C。平均的14C/12C之比等于1.2×10-12。
12C是稳定的,也就是说,随时间推移,给定样品中的12C原子数不变。14C自身是放射性的(生物的每克碳含有足够的14C同位素以产生每分钟13.6次的衰变)并且这种原子在样品中的数量根据以下定律随时间(t)的推移而降低:
n=no exp(-at),
其中:
-no是起始时(生物、动物或植物死亡时)的14C原子数,
-n是经过时间t后的14C原子数,
-a是衰变常数(或放射性常数),其与半衰期有关。
半衰期(或半衰变周期)是给定实体的任意数量的放射性核或不稳定粒子通过衰变减少一半时的时间;半衰期T1/2与衰变常数a通过式aT1/2=ln2相关联。14C的半衰期为5730年。
鉴于14C的半衰期(T1/2),14C的含量从能再生原材料的汲取直至本发明聚酰胺的制造以及甚至直到它们的使用的终结都是基本上恒定的。
本发明聚酰胺包含得自能再生来源的原材料的有机碳(即结合到有机分子中的碳),这可通过根据标准ASTM D6866-06(Standard Test Methods forDetermining the Biobased Content of Natural Range Materials UsingRadiocarbon and Isotope Ratio Mass Spectrometry Analysis)中所述方法之一测定14C的含量来进行鉴定。
该标准ASTM D6866-06包括三种用于测量得自能再生原材料的有机碳(称作基于生物的碳)的方法。用于表示本发明聚酰胺的比例优选根据质谱法或根据标准ASTM D6866-06中所述的液体闪烁光谱法进行测量。
因此,材料中的14C的存在(无论其量的多少)给出了关于其组成分子的来源的指示,即,一些部分不再源自化石材料而是源自能再生的原材料。因此,根据标准ASTM D6866-06中所述的方法进行的测试可将得自能再生材料的起始单体或反应物与得自化石材料的单体或反应物区分开。这些测试起到检验的作用。
因此,当使用得自能再生原材料的二羧酸Y时,所获得的聚酰胺表现出与由得自石化工业的二酸获得的现有技术聚酰胺的机械性能、化学性能和热性能相似的机械性能、化学性能和热性能,这至少符合前面所述的可持续发展的各项要求之一,即,限制化石资源的使用。
植物来源的原材料表现出由基本上具有偶数个碳原子的化合物构成的优点,这与得自石油馏分的单体相反,对所述石油馏分来说,其不但具有含有偶数个碳原子的杂质而且具有含有奇数个碳原子的杂质。因此,在用于转化得自植物来源原材料的产物的过程期间引入的杂质基本上具有偶数个碳原子。这些包含奇数个碳原子的杂质的存在对最终聚酰胺的大分子结构具有直接影响,导致对结构产生干扰(disturbance)的效果。因此,可发现聚酰胺的一些性质(如结晶度、熔点或玻璃化转变温度)由此受到影响。
换句话说,聚酰胺的单体Y得自其自身源自能再生原材料的C12、C14或C16二酸(其鉴定根据标准ASTM D6866进行)。本发明聚酰胺中的能再生有机碳的以百分数表示的含量严格地大于0,该含量以%Crenew.org表示且对应于如下等式(I):
在该等式中,
i=百分之百地由能再生原材料获得的单体,
j=百分之百地由化石原材料获得的单体,
k=部分地由能再生原材料获得的单体,
Fi、Fj、Fk=所述单体i、j和k在所述共聚酰胺中的各自的摩尔分数,
Ci、Cj、Ck=在所述共聚酰胺中的所述单体i、j和k的各自碳原子数,
Ck′=所述单体k中的能再生有机碳原子的数量,
根据标准ASTM D6866的测量方法之一确定单体i、j和k各自的性质(能再生的或化石的),就是说它们各自的来源。
(共聚)单体X和Y为等式(I)含义内的单体i、j和k。
优选地,所述聚酰胺的%Crenew.org含量大于或等于20%,有利地大于或等于40%,优选大于或等于50%,且更优选大于或等于52%。
当本发明聚酰胺表现出大于或等于50%的%Crenew.org含量时,其满足获得JBPA的“Biomass Pla”认证(其也是基于标准ASTM D6866的认证)所需的标准。另外,本发明聚酰胺可有充分的根据带有JORA的“Biomass-based”标志。
例如,(共聚)单体可得自能再生资源例如植物油或天然多糖如淀粉或纤维素,对于淀粉来说,可例如从玉米或马铃薯中提取。这或这些(共聚)单体或原材料不但可特别地源自各种转化过程(特别是传统的化学过程),而且也可源自通过酶路线或通过生物发酵进行转化的过程。
C12二酸(十二烷二酸)可通过十二烷酸(也称作月桂酸)的生物发酵获得,所述月桂酸可例如从由棕榈仁和椰子组成的富油中提取。
C14二酸(十四烷二酸)可通过肉豆蔻酸的生物发酵获得,所述肉豆蔻酸可例如从由棕榈仁和椰子组成的富油中提取。
C16二酸(十六烷二酸)可通过棕榈酸的生物发酵获得,所述棕榈酸例如主要在棕榈油中出现。
例如,为了发生脂肪一元酸向二酸的转化,可使用改性的酵母热带念珠菌(WO91/06660;US4474882)。
本发明聚酰胺的单体X代表脂环族二胺。
在脂环族二胺中,优选包含两个环的那些。具体地说,它们对应于如下通式:
其中
R1~R4表示选自氢原子或具有1~6个碳原子的烷基的相同或不同的基团,X表示单键或由下列物质组成的二价基团:
·包含1~10个碳原子的直链或支链脂族链,
·具有6~12个碳原子的脂环族基团,
·被具有6~8个碳原子的脂环族基团取代的具有1~10个碳原子的直链或支链的脂族链,
·由带有环己基或苄基的直链或支链二烷基组成的具有8~12个碳原子的基团。
更优选地,本发明共聚酰胺的脂环族二胺选自二(3,5-二烷基-4-氨基环己基)甲烷、二(3,5-二烷基-4-氨基环己基)乙烷、二(3,5-二烷基-4-氨基环己基)丙烷、二(3,5-二烷基-4-氨基环己基)丁烷、二(3-甲基-4-氨基环己基)甲烷(BMACM或MACM)、对-二(氨基环己基)甲烷(PACM)和异亚丙基二(环己基胺)(PACP)。
进一步更优选地,和为了得到透明共聚酰胺,所述脂环族二胺选自二(3-甲基-4-氨基环己基)甲烷(BMACM或MACM)(特别是由BASF以商品名C260出售的那些)和对-二(氨基环己基)甲烷(PACM)。
选择这样的脂环族二胺(BACM或PACM20)可在大部分情况下得到透明聚酰胺,其中,透明度通过聚酰胺的熔融焓(其值为0~12J/g)进行表征。
在聚酰胺X.Y的所有可能组合中,特别选择对应于选自式MACM.12、MACM.14、PACM.12或PACM.14之一的聚酰胺。
用于定义聚酰胺的命名法描述于标准ISO 1874-1:1992″Plastics--Polyamide(PA)moulding and extrusion materials--Part 1:Designation″(特别是第3页(表1和表2))中,并且该命名法是本领域技术人员所公知的。
脂环族二胺和二酸的摩尔比例优选是化学计量的。
更具体地说,所述聚酰胺为共聚酰胺且可包含至少两种不同的单元并且可对应于以下通式:
X.Y/Z
在该通式中:
X和Y是如前所定义的,
Z选自得自氨基酸的单元、得自内酰胺的单元、和对应于式(Ca二胺).(Cb二酸)的单元,其中a代表二胺的碳原子数和b代表二酸的碳原子数,a和b各自为4~36。
当Z代表氨基酸时,其可选自9-氨基壬酸、10-氨基癸酸、12-氨基十二烷酸和11-氨基十一烷酸、以及其衍生物,特别是N-庚基-11-氨基十一烷酸。
除了一种氨基酸,也可想到两种、三种或更多种氨基酸的混合物。然而,所形成的共聚酰胺则将分别包含三种、四种或更多种单元。
在可想到的组合中,下列共聚酰胺是特别令人感兴趣的:它们是对应于选自式B.12/11、B.12/12、P.12/11、P.12/12、B.14/11、P.14/11、B.14/12或P.14/12之一的共聚酰胺,数字11表示得自11-氨基十一烷酸的单体,“/”之后的数字12表示得自十二内酰胺的单元,P表示二胺PACM,B表示二胺MACM,单体B或P之后的数字12表示十二烷(C12)二酸,且单体B或P之后的数字14表示十四烷(C14)二酸。
在本发明的有利形式中,Z的摩尔含量为2~80%,脂环族二胺X的摩尔含量为10~49%,且二酸Y的摩尔含量也为10~49%。
应说明,前面各段以及本说明书的下文中所用的表述“在...之间(~)”应理解为包括所提及的各个端值。
这样的摩尔含量的选择在大部分情况下可得到透明共聚酰胺,其中,透明度通过共聚酰胺的熔融焓(其值为0~12J/g)进行表征。
当Z代表内酰胺时,其可选自吡咯烷酮、哌啶酮(piperidinone)、己内酰胺、庚内酰胺(enantholactam)、辛内酰胺、壬内酰胺、癸内酰胺、十一内酰胺和十二内酰胺。
当单元Z为对应于式(Ca二胺).(Cb二酸)的单元时,(Ca二胺)单元具有式H2N-(CH2)a-NH2,此时所述二胺为脂族的且为直链的。
优选地,Ca二胺选自丁二胺(a=4)、戊二胺(a=5)、己二胺(a=6)、庚二胺(a=7)、辛二胺(a=8)、壬二胺(a=9)、癸二胺(a=10)、十一烷二胺(a=11)、十二烷二胺(a=12)、十三烷二胺(a=13)、十四烷二胺(a=14)、十六烷二胺(a=16)、十八烷二胺(a=18)、十八碳烯二胺(a=18)、二十烷二胺(a=20)、二十二烷二胺(a=22)和由脂肪酸获得的二胺。
当二胺为脂环族的时,其选自二(3,5-二烷基-4-氨基环己基)甲烷、二(3,5-二烷基-4-氨基环己基)乙烷、二(3,5-二烷基-4-氨基环己基)丙烷、二(3,5-二烷基-4-氨基环己基)丁烷、二(3-甲基-4-氨基环己基)甲烷(BMACM或MACM)、对-二(氨基环己基)甲烷(PACM)和异亚丙基二(环己基胺)(PACP)。其也可包含下列基于碳的主链:降冰片基甲烷、环己基甲烷、二环己基丙烷、二(甲基环己基)或二(甲基环己基)丙烷。这些脂环族二胺的非穷举性列表在出版物″Cycloaliphatic Amines″(Encyclopaedia of Chemical Technology,Kirk-Othmer,第四版(1992),第386-405页)中给出。
当二胺为芳基芳族二胺时,其选自1,3-二甲苯二胺、1,4-二甲苯二胺、以及它们的混合物。
当(Cb二酸)单体为脂族的且为直链的时,其选自丁二酸(y=4)、戊二酸(y=5)、己二酸(y=6)、庚二酸(y=7)、辛二酸(y=8)、壬二酸(y=9)、癸二酸(y=10)、十一烷二酸(y=11)、十二烷二酸(y=12)、十三烷二酸(y=13)、十四烷二酸(y=14)、十六烷二酸(y=16)、十八烷二酸(y=18)、十八碳烯二酸(y=18)、二十烷二酸(y=20)、二十二烷二酸(y=22)和包含36个碳的二聚体脂肪酸。
前述二聚体脂肪酸是通过包含长烃链的不饱和一元脂肪酸(例如亚油酸和油酸)的低聚或聚合获得的二聚脂肪酸,如文献EP0471566中所具体描述的。
当二酸为脂环族二酸时,其可包含下列基于碳的主链:降冰片基甲烷、环己基甲烷、二环己基甲烷、二环己基丙烷、二(甲基环己基)或二(甲基环己基)丙烷。
当二酸为芳族二酸时,其选自对苯二甲酸、间苯二甲酸和萘二甲酸。
当出现其中Z为(Ca二胺).(Cb二酸)单元且其与共聚单体或单元X.Y严格地相同(即,a=MACM或PACM且Cb=C12、C14或C16)的特定情况时,涉及如前所述的可包含来自于能再生来源和化石来源两者的二酸的均聚酰胺。
在其中Z为(Ca二胺).(Cb二酸)单元的共聚酰胺X.Y/Z的所有可能组合中,特别选择对应于选自式B.12/10.12、.P.12/10.12、B.14/10.14、P.14/10.14、B.12/10.10、P.12/10.10、B.14/10.10或P.14/10.10之一的共聚酰胺。
根据本发明的另一方面,共聚酰胺另外包含至少一种第三共聚单体,且所述共聚酰胺对应于以下通式:
X.Y/Z/A
在该通式中
A选自得自氨基酸的单元、得自内酰胺的单元、和对应于式(Cd二胺).(Ce二酸)的单元,其中d代表二胺的碳原子数,e代表二酸的碳原子数,a和b各自为4~36。
在式X.Y/Z/A中,一方面可参考以上对于(共聚)单体或单元X.Y的描述,另一方面可参考以上对于Z的描述。
在该式中,单元A具有与前述单元Z相同的含义。
在根据最后一种可选择形式的共聚酰胺X.Y/Z/A的所有可能组合中,特别选择对应于选自式B.12/11/P.12、B.12/12/P.12、B.14/11/P.14、B.14/12/P.14、B.12/11/6.10、B.12/12/6.10、P.12/11/6.10、P.12/12/6.10、B.12/11/10.10、B.12/12/10.10、P.12/11/10.10、P.12/12/10.12、B.12/11/10.12、B.12/12/10.12、P.12/11/10.12、P.12/12/10.12、B.14/11/6.10、B.14/12/6.10、P.14/11/6.10、P.14/12/6.10、B.14/11/10.10、B.14/12/10.10、P.14/11/10.10、P.14/12/10.12、B.14/11/10.12、B.14/12/10.12、P.14/11/10.12或P.14/12/10.12之一的共聚酰胺。
单元Z和单元A可源自化石资源或源自能再生资源,从而提高了最终聚酰胺中的有机碳的比例。
本发明还涉及前述聚酰胺的制备方法,该方法包括至少一个将脂环族二胺与至少一种二酸(其包含能再生来源的碳或生物来源的碳)缩聚的步骤。
以上制备方法在上述缩聚步骤之前还可具有下列两个步骤:
a)从能再生原材料如植物油或动物油得到脂肪一元酸;任选地进行纯化,
b)从得自前一步骤的脂肪一元酸制备二酸,例如通过发酵进行制备;
随后,使所述二酸与脂环族二胺缩聚。
本发明还涉及包含至少一种聚酰胺的组合物。
根据本发明的组合物可另外包含至少一种第二聚合物。
有利地,该第二聚合物可选自半结晶聚酰胺、无定形聚酰胺、半结晶共聚酰胺、无定形共聚酰胺、聚醚酰胺、聚酯酰胺、以及它们的共混物。
优选地,该第二聚合物得自能再生原材料,即,符合标准ASTM D6866的测试。
该第二聚合物可具体选自淀粉(可对其进行改性和/或配制(formulate))、纤维素或其衍生物(如醋酸纤维素或纤维素醚)、聚乳酸、聚乙醇酸和聚羟基烷酸酯(polyhydroxyalkanoate)。
根据本发明的组合物也可另外包含至少一种添加剂。
该添加剂可具体地选自填料、纤维、染料、稳定剂特别是UV稳定剂、增塑剂、抗冲改性剂、表面活性剂、颜料、增亮剂、抗氧化剂、天然蜡、以及它们的混合物。
在填料中,可具体提及二氧化硅、炭黑、碳纳米管、膨胀石墨、氧化钛或玻璃珠。
优选地,该添加剂为天然且能再生来源的添加剂,即,符合标准ASTM D6866的测试。
虽然,除了N-庚基-11-氨基十一烷酸、二聚体脂肪酸和脂环族二胺之外,本发明中涉及的共聚单体或原材料(氨基酸、二胺、二酸)实际上(effectively)为直链的,但并不禁止它们可以全部或部分地为支链的(如2-甲基-1,5-二氨基戊烷)或部分不饱和的。
应特别注意,C18二羧酸可为饱和的十八烷二酸、或者其部分表现出不饱和性的十八碳烯二酸。
本发明共聚酰胺或者根据本发明的组合物可用于构成结构体。
当所述结构体仅由共聚酰胺或者仅由根据本发明的组合物形成时,该结构体可以是单层的。
当所述结构体包括至少两层并且当形成该结构体的不同层中的至少一个是由本发明聚酰胺或组合物形成时,该结构体也可以是多层结构体。
具体地说,所述结构体(不论是单层或多层的)可以纤维、膜、管、中空体、注射部件或透镜的形式提供。
本发明聚酰胺或根据本发明的组合物可有利地用于透镜(特别是光学透镜)、眼镜片或眼镜架的制造。
对于本发明聚酰胺或组合物的用途,还可想到用于电气及电子商品(例如电话、计算机或多媒体系统)的全部或部分部件。
本发明聚酰胺和组合物可根据现有技术所述的常规方法进行制造。具体地说,可参考文献DE4318047或US6143862。
现在,以下述实施例描述本发明,所述实施例仅用于说明目的并且很显然不用于进行限定。
实施例
1/不同聚酰胺的制备(试验A~H)
试验A~H中使用的单体如下:
-11-氨基十一烷酸(在表1中表示为A11),由Arkema提供,CAS2432-99-7,
-包含21重量%反/反异构体的对-二(氨基环己基)甲烷(在表1中表示为PACM20),由Air Product以商品名出售,CAS 1761-71-3,
-十二烷二酸(在表1中表示为DC12),得自月桂酸,
-十四烷二酸(在表1中表示为DC14),得自肉豆蔻酸,
-内酰胺12(在表1中表示为L12),由Arkema出售,CAS 947-04-6。
根据表1给出的具体组成(实施例A~H),由两种或三种单体(作为与若干种添加剂的混合物)制备各种均聚酰胺和共聚酰胺。
现在,针对实施例A具体描述制备方法(所述制备方法可适用于所有实施例A~H)。
应说明,以下所示的添加剂的重量含量可适用于所有实施例A~H。
-13.98kg的十二烷二酸(60.82摩尔)
-14.58kg的MACM(61.16摩尔)
-72.17g的苯甲酸(0.59摩尔)
-8.75g的次磷酸(H3PO2)
-525g的蒸馏水
将所述组合物引入到92升高压釜反应器中,闭合该反应器后立刻在搅拌下加热至260℃。在自生压力下保持两小时的阶段(phase)后,以1.5小时将压力降至大气压。然后,该反应器通过用氮气冲洗在280℃脱气约1小时。
然后,将所得的均聚酰胺挤出为带(lace)状,在处于环境温度的水浴中冷却,然后进行造粒。
随后,将所得的颗粒在真空下在80℃干燥12小时以达到小于0.1%的水分含量。
在%Crenew.org含量实际上严格地大于0的意义上,实施例A~H的均聚酰胺和共聚酰胺符合本发明。
此外,实施例A~H的共聚酰胺还是透明的。
此外,已经清晰地描述了包含两种或三种不同单元的共聚酰胺。但是,并不禁止使用包含超过三种不同单元(例如四种或五种不同单元)的共聚酰胺,这些单元各自由氨基酸或者由内酰胺获得或者对应于式(二胺).(二酸),限制条件为聚酰胺包含根据标准ASTM D6866确定的能再生来源的有机碳,换言之,由前述等式(I)确定的%Crenew.org含量严格地大于0。
表1
2/化石和植物来源的二酸样品中所存在的杂质的比例的对比
分析以下二酸的样品:
-根据下述方法制备的十二烷二酸:
可从椰子油或从棕榈仁油中提取月桂酸。随后,可使用合适的微生物从月桂酸开始通过生物发酵得到十二烷二酸。随后,可在氨和至少一种强碱的存在下且不使用溶剂,使所述二酸经历胺化。
-化石来源的十二烷二酸,
-根据以下方法制备的十四烷二酸:
可从椰子油或从棕榈仁油中提取肉豆蔻酸。随后,可使用合适的微生物从肉豆蔻酸开始通过生物发酵得到十四烷二酸。随后,可在氨和至少一种强碱的存在下且不使用溶剂,使所述二酸经历胺化。
-化石来源的十四烷二酸。
所有这些产物预先通过在乙腈、三甲基胺和二(三甲基甲硅烷基)三氟乙酰胺的混合物中进行甲硅烷基化而进行衍生。
通过联用的气相色谱/质谱对所得的每种产物的样品进行半定量分析。所用内标物为Tinuvin 770,且柱子为长50m的CP-SIL 5CB型(Varian)。
该分析可以鉴别出一定数量的脂族二酸类杂质(一些包含偶数个碳原子且另一些包含奇数个碳原子),并且对它们共有的内容物进行半定量比较。
因此,对于所分析的每个样品,计算以下比率R:
R=(含有奇数个碳原子的杂质的量)/(含有偶数个碳原子的杂质的量)
结果示于下表中:
表2
这些分析表明,在植物来源的产物的情况下,包含奇数个碳原子的杂质的比例低得多,这有利于对由这些产物制备的聚酰胺的大分子结构产生较小的干扰。
3/从碳循环离开的大气CO2的评价
在下表中给出了当产生1吨本发明聚酰胺时从碳循环“离开”的大气CO2的量。
表3
B.12 | B.14 | B.16 | |
储存的大气CO2当量/吨PA | 1.22吨 | 1.34吨 | 1.44吨 |
4/可能在寿命结束时释放的CO2的重量的评价
对具有重复单元分子式C27H48N2O2的B.12进行测量,所述重复单元的摩尔质量为432g/mol且碳C的重量为324g/mol,即总的碳百分数=75%。
表4
Claims (16)
1.包含至少一种对应于以下通式的重复单元的聚酰胺:
X.Y
在该通式中:
X代表脂环族二胺,和
Y代表选自十二烷(C12)二酸、十四烷(C14)二酸和十六烷(C16)二酸的脂族二羧酸,
所述聚酰胺的特征在于所述二羧酸包含根据标准ASTM D6866确定的能再生来源的有机碳。
2.权利要求1的聚酰胺,特征在于所述聚酰胺包含大于或等于20%、有利地大于或等于40%、优选大于或等于50%、且更优选大于或等于52%的以百分数表示的能再生来源的有机碳的含量,该含量以%Crenew.org表示。
3.前述权利要求中任一项的聚酰胺,特征在于所述聚酰胺为均聚酰胺。
4.前述权利要求中任一项的聚酰胺,特征在于所述单体X选自3,3’-二甲基-4,4’-二氨基二环己基甲烷(BMACM或MACM)和对-二(氨基环己基)甲烷(PACM)。
5.前述权利要求中任一项的聚酰胺,特征在于其具有式MACM.12、MACM.14、PACM.12或PACM.14。
6.权利要求1~5中任一项的聚酰胺,特征在于其为对应于以下通式的包含至少两种不同单元的共聚酰胺:
X.Y/Z
在该通式中:
X和Y是如前述权利要求中任一项所定义的,
Z选自得自氨基酸的单元、得自内酰胺的单元、和对应于式(Ca二胺).(Cb二酸)的单元,其中a代表二胺的碳原子数和b代表二酸的碳原子数,a和b各自为4~36。
7.权利要求6的聚酰胺,特征在于其为选自具有下式共聚酰胺的共聚酰胺:B.12/11、B.12/12、P.12/11、P.12/12、B.14/11、P.14/11、B.14/12、P.14/12、B.12/10.12、P.12/10.12、B.14/10.14、P.14/10.14、B.12/10.10、P.12/10.10、B.14/10.10和P.14/10.10,B表示3,3’-二甲基-4,4’-二氨基二环己基甲烷且P表示对-二(氨基环己基)甲烷。
8.用于制备前述权利要求中任一项的聚酰胺的方法,包括至少一个使脂环族二胺与至少一种脂肪二酸缩聚的步骤,所述脂肪二酸包含根据标准ASTM D6866确定的能再生来源的碳。
9.包含至少一种根据权利要求1~7中任一项的聚酰胺的组合物。
10.权利要求9的组合物,特征在于其另外包含至少一种选自半结晶或无定形聚酰胺、半结晶或无定形共聚酰胺、聚醚酰胺、聚酯酰胺、以及它们的共混物的第二聚合物。
11.权利要求9或10的组合物,特征在于所述第二聚合物得自根据标准ASTM D6866确定的能再生原材料。
12.权利要求9和10中任一项的组合物,特征在于其另外包含至少一种添加剂,优选为根据标准ASTM D6866确定的天然的且能再生来源的添加剂,所述添加剂选自填料、纤维、染料、稳定剂特别是UV稳定剂、增塑剂、抗冲改性剂、表面活性剂、颜料、增亮剂、抗氧化剂、天然蜡、以及它们的混合物。
13.权利要求1~7中任一项的聚酰胺或者权利要求9~12中任一项的组合物在构成单层结构体或多层结构体的至少一层中的用途。
14.权利要求13的用途,特征在于所述结构体以纤维、膜、管、中空体或注射部件的形式提供。
15.权利要求1~7中任一项的聚酰胺或者权利要求9~12中任一项的组合物在透明制品的制造中的用途。
16.权利要求1~7中任一项的聚酰胺或者权利要求9~12中任一项的组合物在透镜、眼镜片或眼镜架的制造中的用途。
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BRPI0915299A8 (pt) | 2018-10-09 |
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KR20110033136A (ko) | 2011-03-30 |
WO2009153531A1 (fr) | 2009-12-23 |
US9599512B2 (en) | 2017-03-21 |
TWI612076B (zh) | 2018-01-21 |
FR2932807B1 (fr) | 2011-12-30 |
KR101680386B1 (ko) | 2016-11-28 |
EP2294111A1 (fr) | 2011-03-16 |
BRPI0915299B1 (pt) | 2019-02-26 |
US20110111154A1 (en) | 2011-05-12 |
EP2294111B1 (fr) | 2018-07-25 |
FR2932807A1 (fr) | 2009-12-25 |
BRPI0915299A2 (pt) | 2016-02-16 |
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